US4277588A - Preparation of acetylene copolymers - Google Patents
Preparation of acetylene copolymers Download PDFInfo
- Publication number
- US4277588A US4277588A US06/129,828 US12982880A US4277588A US 4277588 A US4277588 A US 4277588A US 12982880 A US12982880 A US 12982880A US 4277588 A US4277588 A US 4277588A
- Authority
- US
- United States
- Prior art keywords
- acetylene
- carbonyl
- dialkynes
- polyalkynes
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F238/00—Copolymers of compounds having one or more carbon-to-carbon triple bonds
Definitions
- the present invention relates to the preparation of acetylene copolymers by polymerizing mixtures of acetylene and dialkynes or polyalkynes with Ziegler catalysts.
- the present invention relates to a process for the preparation of acetylene copolymers by catalytic polymerization of acetylene with Ziegler catalysts, wherein mixtures of acetylene and dialkynes or polyalkynes are polymerized.
- Suitable comonomers to use with acetylene are butadiyne, hexadiyne, octadiyne, diethynylbenzene, 1,3,5-triethynylbenzene, 1,2,4-triethynylbenzene, 1,3,5-tris-trimethylsilyl-ethynyl-2,4,6-trimethylsilylbenzene and 1,3,5-tris-propyn-1-yl-2,4,6-trimethylbenzene.
- monomer mixtures which contain up to 50 mole % of dialkynes or polyalkynes, preferably from 5 to 20 mole % of dialkynes or polyalkynes, are used.
- the polymerization is most advantageously carried out with Ziegler catalysts which have been prepared from mixtures of aluminum-trialkyls and titanium tetraoxyalkyls.
- suitable aluminum-trialkyls are aluminum-triethyl, aluminum-triisobutyl and aluminum-trioctyl, the last-mentioned being preferred.
- the titanium tetraoxyalkyls used are advantageously those where alkyl is of 1 to 10 carbon atoms; in particular, titanium tetraoxybutyl has proved suitable.
- the weight ratio of aluminum-trialkyl to titanium tetraoxyalkyl in the mixture is from 0.5:1 to 1:0.5, preferably about 1:1.
- Metal carbonyls eg. iron carbonyl, nickel carbonyl, manganese carbonyl, cobalt carbonyl or molybdenum carbonyl, may also be added to the Ziegler catalysts.
- the weight ratio of metal carbonyls to aluminum-trialkyl in the mixture is from 0.5:1 to 1:0.5, preferably 1:1.
- the catalyst mixture is used in an amount of from 0.1 to 10 parts per 100 parts of the mixture of acetylene and other alkynes.
- the polymerization temperature is advantageously from -90° to +100° C., preferably from -30° to +30° C.
- the polymerization is advantageously carried out at from 0.1 to 500 bar, preferably at about 50 bar.
- the polymerization can for example be carried out in an auxiliary fluid.
- Suitable materials are fluids which are inert toward the polymerization catalysts and toward the monomers, eg. aliphatic oils, aromatics and cycloaliphatics, but also petroleum ether, naphtha and cyclopentadiene.
- the auxiliary fluids are employed in a weight ratio of the alkynes of from 1:1 to 1,000:1, preferably a ratio of the order of 10:1.
- the catalysts may be introduced initially, together with the auxiliary fluid, and/or be added continuously during the polymerization.
- the process gives copolymers of acetylene with dialkynes or polyalkynes which are virtually insoluble.
- the novel polymers may be used as colored pigments or, because of their film-forming tendency, as colored coatings on metals, glass or plastics; they are also of interest because of their electrical and magnetic properties.
- a 500 ml vessel was evacuated and flushed with nitrogen, after which 100 mlof toluene and 20 ml of the above catalyst solution were introduced.
- the reaction vessel was cooled to -50° C. After this temperature had been reached, mixtures of acetylene with various amounts of dialkynes of polyalkynes were introduced into the fluid. After the polymerization had ended, the fluid was siphoned from the reaction vessel and the mixture from the reaction vessel was suction-filtered. The resulting copolymers were washed and dried.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2912572 | 1979-03-29 | ||
DE19792912572 DE2912572A1 (de) | 1979-03-29 | 1979-03-29 | Verfahren zur herstellung von copolymerisaten des acetylens |
Publications (1)
Publication Number | Publication Date |
---|---|
US4277588A true US4277588A (en) | 1981-07-07 |
Family
ID=6066849
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/129,828 Expired - Lifetime US4277588A (en) | 1979-03-29 | 1980-03-13 | Preparation of acetylene copolymers |
Country Status (3)
Country | Link |
---|---|
US (1) | US4277588A (de) |
EP (1) | EP0017133B1 (de) |
DE (2) | DE2912572A1 (de) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58145420A (ja) * | 1981-11-20 | 1983-08-30 | ザ・ブリテイツシユ・ペトロレアム・コンパニ−・ピ−・エル・シ− | コヒ−レントなポリ(アセチレン)フイルムの製法 |
US4408027A (en) * | 1980-08-09 | 1983-10-04 | Bayer Aktiengesellschaft | Foils of polyacetylene |
US4454178A (en) * | 1981-11-05 | 1984-06-12 | Basf Aktiengesellschaft | Poly(acetylene) films and their production |
US4481312A (en) * | 1981-04-02 | 1984-11-06 | Bayer Aktiengesellschaft | Sheet structures and fibers containing burr-shaped or fibrous, doped polyacetylene particles and process for the production thereof |
US4564492A (en) * | 1983-04-08 | 1986-01-14 | The British Petroleum Company, P.L.C. | Polyacetylene production |
US4579921A (en) * | 1983-11-29 | 1986-04-01 | Societe Nationale Elf Aquitaine | Process for the manufacture of polyacetylene |
US4857490A (en) * | 1987-08-31 | 1989-08-15 | Hoechst Celanese Corp. | Process of manufacturing boron ceramics from carboralated diacetylene polymers |
US4946919A (en) * | 1987-08-31 | 1990-08-07 | Hoechst Celanese Corp. | Boron ceramics from carboralated diacetylene polymers |
US5028354A (en) * | 1987-10-05 | 1991-07-02 | Regents Of The University Of California | Conductive articles of intractable polymers method for making |
US5091488A (en) * | 1984-11-30 | 1992-02-25 | Director-General Of Agency Of Industrial Science And Technology | Polyethylacetylene derivative and process for preparation thereof |
US5216102A (en) * | 1988-08-05 | 1993-06-01 | Matsushita Electric Industrial Co., Ltd. | Process for producing polyacetylene |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3113331A1 (de) * | 1981-04-02 | 1982-10-28 | Bayer Ag, 5090 Leverkusen | Kletten- bzw. faserfoermige, dotierte polyacetylenteilchen enthaltende thermoplastische kunststoffe und verfahren zu ihrer herstellung |
DE3120441A1 (de) * | 1981-05-22 | 1982-12-09 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von filmfoermigem poly(acetylen) |
US4394304A (en) * | 1982-01-29 | 1983-07-19 | Massachusetts Institute Of Technology | Electrically conducting polymer blends |
DE3207857A1 (de) * | 1982-03-05 | 1983-09-15 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von poly(acethylen)filmen |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB901326A (en) * | 1959-04-01 | 1962-07-18 | American Cyanamid Co | Polymers and copolymers of diacetylenes |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL208266A (de) * | 1955-03-18 | |||
US4020265A (en) * | 1971-02-24 | 1977-04-26 | General Electric Company | Polyacetylene tetrapolymers |
US4108942A (en) * | 1972-03-22 | 1978-08-22 | General Electric Company | Polyphenylene polymers and methods for making the same |
-
1979
- 1979-03-29 DE DE19792912572 patent/DE2912572A1/de not_active Withdrawn
-
1980
- 1980-03-13 US US06/129,828 patent/US4277588A/en not_active Expired - Lifetime
- 1980-03-25 DE DE8080101560T patent/DE3061394D1/de not_active Expired
- 1980-03-25 EP EP80101560A patent/EP0017133B1/de not_active Expired
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB901326A (en) * | 1959-04-01 | 1962-07-18 | American Cyanamid Co | Polymers and copolymers of diacetylenes |
Non-Patent Citations (4)
Title |
---|
J. Chem. Soc. Chem. Comm., (1977), p. 578 et seq. * |
J. Chem. Soc. Japan, Ind. Chem. Sec. 65, (1962), p. 723 et. seq. * |
Journal of Pol. Sci. Part A-1, 10, 2033-2043, (1972). * |
Trans. Farad. Soc. 64, (1968), p. 823, et. seq. * |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4408027A (en) * | 1980-08-09 | 1983-10-04 | Bayer Aktiengesellschaft | Foils of polyacetylene |
US4481312A (en) * | 1981-04-02 | 1984-11-06 | Bayer Aktiengesellschaft | Sheet structures and fibers containing burr-shaped or fibrous, doped polyacetylene particles and process for the production thereof |
US4454178A (en) * | 1981-11-05 | 1984-06-12 | Basf Aktiengesellschaft | Poly(acetylene) films and their production |
JPH0440371B2 (de) * | 1981-11-20 | 1992-07-02 | Buriteitsushu Pitorooriamu Co Plc Za | |
US4496702A (en) * | 1981-11-20 | 1985-01-29 | The British Petroleum Company P.L.C. | Polyacetylene production |
JPS58145420A (ja) * | 1981-11-20 | 1983-08-30 | ザ・ブリテイツシユ・ペトロレアム・コンパニ−・ピ−・エル・シ− | コヒ−レントなポリ(アセチレン)フイルムの製法 |
US4564492A (en) * | 1983-04-08 | 1986-01-14 | The British Petroleum Company, P.L.C. | Polyacetylene production |
US4579921A (en) * | 1983-11-29 | 1986-04-01 | Societe Nationale Elf Aquitaine | Process for the manufacture of polyacetylene |
US5091488A (en) * | 1984-11-30 | 1992-02-25 | Director-General Of Agency Of Industrial Science And Technology | Polyethylacetylene derivative and process for preparation thereof |
US4946919A (en) * | 1987-08-31 | 1990-08-07 | Hoechst Celanese Corp. | Boron ceramics from carboralated diacetylene polymers |
US4857490A (en) * | 1987-08-31 | 1989-08-15 | Hoechst Celanese Corp. | Process of manufacturing boron ceramics from carboralated diacetylene polymers |
US5028354A (en) * | 1987-10-05 | 1991-07-02 | Regents Of The University Of California | Conductive articles of intractable polymers method for making |
US5216102A (en) * | 1988-08-05 | 1993-06-01 | Matsushita Electric Industrial Co., Ltd. | Process for producing polyacetylene |
Also Published As
Publication number | Publication date |
---|---|
DE2912572A1 (de) | 1980-10-09 |
EP0017133A1 (de) | 1980-10-15 |
DE3061394D1 (en) | 1983-01-27 |
EP0017133B1 (de) | 1982-12-22 |
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Legal Events
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STCF | Information on status: patent grant |
Free format text: PATENTED CASE |